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The photoelectric effect provides evidence for the particle nature of light.
It also provides evidence for quantization.
Einstein assumed that light traveled in energy packets called photons.
The energy of one photon is E = h.
Light shining on the surface of a metal can cause electrons to be ejected from the metal.
The electrons will only be ejected if the photons have sufficient energy (work function):
Below the threshold frequency no electrons are ejected.
Above the threshold frequency, the excess energy appears as the kinetic energy of the ejected electrons.
Light has wave-like AND particle-like properties.
When radiation from a light source, such as a lightbulb, is separated into its different wavelength components, a
spectrum is produced.
White light can be separated into a continuous spectrum of colors.
A rainbow is a continuous spectrum of light produced by the dispersal of sunlight by raindrops or mist.
On the continuous spectrum there are no dark spots, which would correspond to different lines.
Not all radiation is continuous.
A gas placed in a partially evacuated tube and subjected to a high voltage produces single colors of light.
The spectrum that we see contains radiation of only specific wavelengths; this is called a line spectrum.
Bohrs Model
Rutherford assumed that electrons orbited the nucleus analogous to planets orbiting the sun.
However, a charged particle moving in a circular path should lose energy.
This means that the atom should be unstable according to Rutherfords theory.
Bohr noted the line spectra of certain elements and assumed that electrons were confined to specific energy states.
These were called orbits.
Bohrs model is based on three postulates:
Only orbits of specific radii, corresponding to certain definite energies, are permitted for electrons in an atom.
An electron in a permitted orbit has a specific energy and is an "allowed" energy state.
Energy is only emitted or absorbed by an electron as it moves from one allowed energy state to another.
The energy is gained or lost as a photon.
Colors from excited gases arise because electrons move between energy states in the atom.
Since the energy states are quantized, the light emitted from excited atoms must be quantized and appear as line
spectra.
Bohr showed mathematically that
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E (hcRH ) 2 (2.18 1018 J) 2
n
n
where n is the principal quantum number (i.e., n = 1, 2, 3, ) and RH is the Rydberg constant.
The product hcRH = 2.18 10-18 J.
The first orbit in the Bohr model has n = 1 and is closest to the nucleus.
The furthest
orbit in the Bohr model has n = and corresponds to E = 0.
Electrons in the Bohr model can only move between orbits by absorbing and emitting energy in quanta (E = h.
The ground state is the lowest energy state.
An electron in a higher energy state is said to be in an excited state.
The amount of energy absorbed or emitted by moving between states is given by
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E E f Ei h 2.18 1018 J 2 2
n
f ni
Knowing that light has a particle nature, it seems reasonable to ask whether matter has a wave nature.
This question was answered by Louis deBroglie.
Using Einsteins and Plancks equations, deBroglie derived:
h/m
The square of the wave function, , gives the probability of finding the electron.
If we solve the Schrdinger equation we get wave functions and energies for the wave
functions.
We call orbitals.
Schrdingers equation requires three quantum numbers:
Principal quantum number, n. This is the same as Bohrs n.
As n becomes larger, the atom becomes larger and the electron is further from the nucleus.
Angular momentum quantum number, l. This quantum number depends on the value of n.
The values of l begin at 0 and increase to n 1.
We usually use letters for l (s, p, d and f for l = 0, 1, 2, and 3). Usually we refer to the s, p, d and f orbitals.
This quantum number defines the shape of the orbital.
Magnetic quantum number, ml.
This quantum number depends on l.
The magnetic quantum number has integer values between l and +l.
There are (2l+1) possible values of ml.
For example, for l = 1, there are (21+1) = 3 values of ml : 0, +1, and -1.
Consequently, for l = 1, there are 3 orbitals: px, py and pz.
Magnetic quantum numbers give the three-dimensional orientation of each orbital.
A collection of orbitals with the same value of n is called an electron shell.
There are n2 orbitals in a shell described by a the n value.
For example, for n = 3, there are 32 = 9 orbitals.
A set of orbitals with the same n and l is called a subshell.
Each subshell is designated by a number and a letter.
For example, 3p orbitals have n = 3 and l = 1.
There are n types of subshells in a shell described by a the n value.
For example, for n = 3, there are 3 subshells: 3s, 3p and 3d.
Orbitals can be ranked in terms of energy to yield an Aufbau diagram.
Note that this Aufbau diagram is for a single electron system.
As n increases, note that the spacing between energy levels becomes smaller.
The p Orbitals
Line spectra of many electron atoms show each line as a closely spaced pair of lines.
Stern and Gerlach designed an experiment to determine why.
A beam of atoms was passed through a slit and into a magnetic field and the atoms were then detected.
Two spots were found: one with the electrons spinning in one direction and one with the electrons spinning in
the opposite direction.
Since electron spin (electron as a tiny sphere spinning on its own axis) is quantized,
We define ms = spin magnetic quantum number = 1/2.
Paulis exclusion principle states that no two electrons can have the same set of 4 quantum numbers.
Therefore, two electrons in the same orbital must have opposite spins.
Electron configurations tell us how the electrons are distributed among the various orbitals of an atom.
The most stable configuration, or ground state, is that in which the electrons are in the lowest possible energy state.
When writing ground-state electronic configurations:
electrons fill orbitals in order of increasing energy with no more than two electrons per orbital.
no two electrons can fill one orbital with the same spin (Pauli).
for degenerate orbitals, electrons fill each orbital singly before any orbital gets a second electron.
How do we show spin?
An arrow pointing upwards has ms = + 1/2 (spin up).
An arrow pointing downwards has ms = 1/2 (spin down).
Hund's Rule
Hunds rule: for degenerate orbitals, the lowest energy is attained when the number of electrons with the same spin
is maximized.
Thus, electrons fill each orbital singly with their spins parallel before any orbital gets a second electron.
By placing electrons in different orbitals, electron-electron repulsions are minimized.
Electron configurations may be written using a shorthand notation (condensed electron configuration):
Write the valence electrons explicitly.
Valence electrons are electrons in the outer shell.
These electrons are gained and lost in reactions.
Write the core electrons corresponding to the filled noble gas in square brackets.
Core electrons are electrons in the inner shells.
These are generally not involved in bonding.
Example:
2 2
6 2
3
P is 1s 2s 2p 3s 3p ,
2 2
6
but Ne is 1s 2s 2p .
Therefore, P is [Ne]3s23p3.
Transition Metals
There are many elements that appear to violate the electron configuration guidelines.
Examples:
Chromium is [Ar]3d54s1 instead of [Ar]3d44s2.
Copper is [Ar]3d104s1 instead of [Ar]3d94s2.
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Half-full (d ) and full (d10) d subshells are particularly stable.
Selected Problems:18, 19, 23, 35, 43, 51, 53, 55, 61, 69, 71, 72, 73, 74.
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